Azo-dyes from ether-arylides of amino-hydroxydiaryls



Patented Aug. 16, 1932 UNITED STATES MICHIGAN i nzonxns riioiu nrnnn-nnxmnns or AMINo-HYDnoxx iAnYLs No Drawing. i

aromatic amines into naphthol AS, the latter being 2.3. hydroxynaphthoic ,acid anilide, or byusing related compounds. We have now discovered; that ethers of amino hydr oxy diaryls may beemployed as arylidecomp nents, and furthermorethat diazotiz ed orpolyazotized aromatic amino I compounds may be coupled into arylidesi derived from such amino-ethers and hydroxy-aromatic acids, more particularly 2.3-hydroxy-naphthoic acid, by condensation or other suitable manner', whereby useful azodyes may be formed. The probable formula of such dyes'may be represented as i I hereinafter fully described 7 and particularly pointed out in the claims, the followingdescription setting forth but several of the various ways in which the principle of the invention may be used.

fAmilication filie d Quiy' i, 1929. seriaiNd; 375,327.

ERNEST F. GRETHER 'AND GERALD H. coLnMAN, or m DnAND, MI HIGAN, ASSIGNOR TO THE nowennnrcsn COMPANY, or MIDLAND, MICHIGAN, A CORPORATION, or;

The herein describednew azodyes may be T I prepared from diazo components and the above? mentioned hydroxy aromatic acid arylides many of the ordinary ways. :It is immaterial whether thedyes are applied by developing on' the fiber, by printing a diazo; solution upon padded goods according -;to the well-known method, by using nitrosamine salts of the corresponding bases, or are prepared in substance for use as pigments, in which latter case the respective reaction components may be brought together directly, with or without the aid of a diluting or sol- Z vent medium,'.the-dyebeing separated from the reaction mixture by any suitable means. Mordanting' or other auxiliarytreatment for promoting the absorption of the dye on the Iiber, or after-treatment with metallic salts such as chromium, copper or aluminum salts, I'orfixing the dyev or modifying its color tone may beioptionally employed in conjunction with the dyeing operation Without-departing from the spirit of the invention which is intended to include not ;only the dyes them,- selves but also'material dyed therewith. i

A preferred manner in which our invention may becarried out isillustrated in the following specific examples, it being understood that such examples, however, are not to be interpreted as a limitation upon the'inventiOIl; i

7 Example 1 If The,2.3-hydroxynaphthoic acid arylide of. ,3

3-amino-4-methoxy-diphenyl is prepared by condensing said acid and amine with the aid of phosphorus trichloride the presence of toluene in the usual manner whereby the desired arylide formsasia solid phase intermixed with the liquid medium. The purified arylide has a meltingpointof 'Cotton yarn is impregnated with a alkaline solution of the above arylide to which may be added advantageously, but not necessarily, formaldehyde and/ or other fixative, e. g. Turkey red oil or an aluminum salt.

Said yarn is then immersed in a diazo solution derived from 2-amino-diphenylether.

The dye develops on the fiber, and has a scarlet color, the probable formula being i 1 E'aaa'mipl e 2 In a manner-similar to that: described in Example 1, 'tetrazotized benzidine is coupled into the same arylide, the dyes 1 developing on the fiber, being ora violet blue color and having'the probable formula firm a I,

v The ee-h aeex na hthoieaeidarylid-e of 3 amino l ethoxy-diphenyl P.-210 is 'pre'p'aredand coupled With'te'trazotized 4.4-diamino-di henyl etheri' The dyes which i 5 is developedon the fiber, is bluish rose red in color and ha's'the probable formula m Example 1 a V The 2.3-hydroxynaphthoic acid arylide of 5-amino-2-methoxy diphenyl (M. P. approxi mately 193 is prepared and coupled '35 with dia'zotized' orthomitro: ara-phenetidine.

i J amino -naphthyl-phenyl ether, orthochlo're "type hereindescribed.

The dye is reddish" violet in color and has the probable formula Dianisidine is tetrazotized and coupled into'the arylide repared'inExample 4. The developed dye is blue'and has the probable "formulae- In a similar fashion we have prepared other, dyes of the same general type from the above-mentioned arylides by coupling thereinto other diazotiZed or polya'zotized aromatic amino compounds, e. g; meta nitraniline,

para-nitro-aniline, ortho-alnino 'Vdiphen'yl ether, parahmino-aetanilide, alpha-'naph th'ylamine,z 3-"4-.dichloraniline, ortho-nitro para phen'etidiiie, dianisidine, diamino-di phenyl -ether, benzidine, 'para-chlonorthm toluidine, amino a'z'obe'nzen'e a'ndother aminoazoscompounds. r f

The colors 'of the dyes of the present invention vary from orange to blue, depending on the specific diazo-eomponent employed.

While in the examples, cotton .fibers have been referred to as the material to be dyed wlth the hereindescribedne'w dyes, other natural or synthetic fibers may likewise be dyed fliierewith, such as wool, silk, rayon and the Furthermore, We do notlimi't the invention to the use'ofthe specifically aforementioned intermediates. As diam-component's, any dlazotized or polyazotized aromatic aminoor poly-faminocompounds or their substitution products or derivatives suitable for use in preparing azo-"dyes, may be employed for coupling into the arylides oif the As aZo-fcomponents into which the" abovementioned diam-component's may be coupled, ar'ylides derived from other aminoethers may be utilized,'i. 'e. a1k i,'ary1 or 'aral- 1 likewise may be employedxas "arylide components. In other words, our invention in kyl ethers of amino-hydroxydiaryls or their substitution products, such as the halogen, nitro or other derivatives. Other hydroxyaromatic acids than those specifically herein mentioned,'or'their substitution products, e. g. halogen, nitro or alkyl derivatives,

its broader aspects covers arylides of the general formula I wherein Xrepresents the residue from any:

droxy aromatic acid, R" the residue from an amino-diaryl and R analkyl; aryl'or afrallfiyl group, as well as azo dyes derived there rom.

Other modes of applying the principle of our invention may be employed instead of the one explained, change being made as regards the materials employed, provided the ingredients stated by any of the following claims or the equivalent of such stated in V gredients be employed.

We therefore particularly point out and distinctly claim as our invention 1. A process for the manufacture of new azo dyes which comprises coupling an alkyl ether of a 2.3-hydr0Xy-naphthoyl-aminorhydroxydiphenyl of the generalformula :V

(|J- A1kyl s with a diazotized aromatic amino compound. 2. As new products, the herein'described azo-dyes probably having the general for mula: 1

OH i i O'Alky1 R ooNH i wherein R represents an aromatic residue from adlazotlzed aromatic ammo compound and n is the numberof azo groups linked 3. As a new product, an azo dye produced 7 of 2.3-hydroXy-naphthoic acid, having b; ly/the general formula j a diazotized aromatic amino compound. 51 A process for themanufacture of. new azo dyeswhichcomprises coupling an arylide of 2.3-hydroxy naphthoic-acid, haying ably the formula with a diazotized aromatic -amino compound.

6. A process for the manufacture of new azo dyes which comprisescoup'ling an arylide of 2.3-hydroXy-naphthoic acid, having prob ably the formula with a diazotized aromatic amino compound;

7. A process for the manufacture'ofnew azo dyes which comprises coupl-ingan arylide of 2.3-hydroxy-naphthoic acid, having probably the formula with a diazotized aromatic amino compound. 8.1 A process for .themanufacture; of new azo dyes which comprises couplingan'arylide or rQB-hydroXy-naphthOi acid,; havin probably the formulamm 3 with a diazotized aromatic amino compound. 9. Aprocfess forthe-manufacture of new azo dyes which comprises coupling an arylide of i y rof y- 'ap t e a d, vi pr b ably theformula j; 1

OONH with aidiazotized aromatic. amino compound. '10. As a new product, an azo dye having probablythe general formula r wherein R represents an aryl residue of a diazotized aromatic amino compound and n is the integer 'l.o r 2.

11. Asa new product, an azo dye having probably ,theformula V wherein R representsuan aryl"residue of a diazotizeel aromaticamino compound and n is the 'integer l or s2.= r

* robably the formula j. 4

1.12; As anevvproduct, an azd dye having wherein R represents'an aryl residue of a diazotized aromatic aminocompound and n lSthG integer 1' or 2. or 13,; ,As a new product; 311 3 20 dye having probably the formula f wherein R represents an aryl residue of a diazotized aromatic amine compound and n isthe integer 1 or 2. r Y

14. As-a 'newproduct, an azo' probably the formula v N=N dye having wherein R represents an aryl residue of a diazotized aromatic amino compound and n is the integer 1 or 2. 1

15. As a new compound, an azo dye having probably theformula r I wherein R, represents an aryl residue of a 12 diazotizedarohaatioamino compound and n is the integer 1 or I Signed by us this 28 day of June, 1929.

: a V ERNEST F; GRETI-IER.

GERALD H. COLEMAN.

Certificate of Correction Patent No. 1,871,514. August 16, 1982.

ERNEST F. GRETHER ET AL.

It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page 1, lines 29 to 32, strike out the formula and insert instead:

/N=N x on R comm or," 11

page 2, line 43, for dyes read dye; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 25th day of October, A. D. 1932.

[SEAL] M. J. MOORE,

Acting Gommt'ssioner of Patents. 

